EP0731833B1 - Granular alkali metal nitrilotriacetate - Google Patents
Granular alkali metal nitrilotriacetate Download PDFInfo
- Publication number
- EP0731833B1 EP0731833B1 EP95904155A EP95904155A EP0731833B1 EP 0731833 B1 EP0731833 B1 EP 0731833B1 EP 95904155 A EP95904155 A EP 95904155A EP 95904155 A EP95904155 A EP 95904155A EP 0731833 B1 EP0731833 B1 EP 0731833B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nta
- alkali metal
- granules
- granular
- range
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
Definitions
- This invention relates to processes for the preparation of granular alkali metal nitrilotriacetate and, in particular, to processes for preparing highly absorptive granular alkali metal nitrilotriacetate.
- the invention also relates to the highly absorptive, granular alkali metal nitrilotriacetate product.
- Water-soluble salts of nitrilotriacetic acid are desirable detergent builders in formulations without phosphate builders.
- the powder form of the material tends to cake and there is little absorptivity.
- Detergent builders which absorb liquids have become desirable in recent years as a formulating tool which allows surfactant to be incorporated into a detergent formulation by way of being absorbed into the builder component.
- NTA alkali metal nitrilotriacetate
- a composite detergent granulated product containing from about 3% to about 20% NTA and an inorganic salt selected from the group consisting of sodium metasilicate, sodium carbonate, and sodium sulfate is disclosed in U.S. 3,901,831.
- aqueous NTA is added to an agitated bed of inorganic salt having an initial temperature of from about 300°C to about 550°C so as to cool the bed to below 300°C.
- the bed is then dehydrated at a temperature of about 120°C.
- a process for producing granular products containing disodium nitrilotriacetate is described in U.S. 3,546,123 wherein various acids are employed to wet trisodium nitrilotriacetate followed by agglomeration of the moistened particles and then drying the agglomerated particles to produce a product having a particle size in the range of smaller than a 4 mesh screen and larger than an 80 mesh screen and a density of from about 0.4g/cc to about 0.8g/cc.
- This type of product is obtained conveniently by contacting the NTA powder in a single step with a an aqueous alkali metal silicate solution, mixing the wetted NTA to form granules and then drying the granules whereby a majority of the granules, by weight, are in the -12 to +80 mesh size range, which have a density of at least about 0.60g/cc and an absorptivity in an absorptivity test in the range of above 7 ml/100g.
- a highly absorptive, granular NTA having a density of from 0.60g/cc to 0.81g/cc, and preferably from 0.7 g/cc to 0.81 g/cc; an absorptivity of surfactant in the range of from 7 ml/100g to 20 ml/100g, and preferably in the range of from 12 ml/100g to 18 ml/100g; and a particle size distribution wherein a majority of the granules are within a range of from -12 to +80 U.S. mesh size.
- NTA shall mean the alkali metal salt of nitrilotriacetic acid.
- Trisodium nitrilotriacetate monohydrate sold commercially in powder form by Monsanto Company, is the preferred alkali metal salt of nitrilotriacetic acid, but other alkali metal salts of nitrilotriacetic acid may be used.
- the two-step method of adding the sulfuric acid wherein a portion is added in the dilute aqueous form and the remainder in concentrated form, it has been found that the addition time/mixing time ratio is relaxed such that ratios as low as 0.15 can be employed while still achieving the desired density, particle size distribution and the desired absorptivity of surfactant in the range of from about 12 to 14ml/100cc. It is critical in the two-step method that the dilute acid be added first followed by the remainder in concentrated form.
- the concentration of the dilute aqueous sulfuric acid employed in the two step method is typically in the range of from 2% to 25% while the concentrated acid is typically oleum above 90% and usually having a concentration of 98%.
- NTA Treatment of NTA with an aqueous solution of sulfuric acid results in at least a partial neutralization of the NTA. In most instances the NTA will be neutralized to the disodium nitrilotriacetic acid.
- the amount of acid added to the NTA is essentially the same whether the single or two-step procedure is followed.
- the mole ratio (total) of acid to NTA is typically in the range of from 0.17 to 0.3. More preferably, the total amount of acid added to the dry NTA is in the range of from 0.03 moles to 0.09 moles.
- the mole ratio amount of acid to NTA added in dilute form is typically in the range of from 0.007 to 0.05 and the amount added in the concentrated form is in the range of from 0.02 mole to 0.28 of acid per mole of NTA.
- the addition of the aqueous alkali metal silicate solution in accordance with this invention does not cause a partial neutralization of the NTA.
- Sodium is the preferred alkali metal for both the alkali metal nitrilotriacetate and the alkali metal silicate.
- other alkali metals may be used and aqueous sodium silicates other than the preferred RU® Silicate may also be used.
- the ratio of the alkali metal silicate to the NTA, by weight, is preferably within the range of from 0.17 to 0.40 and the ratio is more preferably within the range of from 0.25 to 0.35.
- the mixing operation can take any form including high, low and non-shear methods. Mixing provides a uniform treatment of the NTA as well as initiating the formation of granules. It has been found that granulated NTA produced in accordance with this invention has low frangibility, high absorptivity and uniform density in the medium density range of at least 0.7g/cc. In addition, the product is free-flowing and exhibits minimum caking and dusting. These properties are highly desired if the granular product is to be accepted for use in the production of detergent formulations. Typical means for mixing the NTA with acid or silicates in accordance with this invention are commercially available blenders and mixers.
- the acid or the silicate solution is typically sprayed onto an agitated mass of NTA.
- Mixing in accordance with this invention may take place in a rotary dryer, drum or the like.
- Typical commercially available mixing apparatus are those manufactured by Stephan Machine Corporation, Columbus, Ohio; Marion Mixers, Marion, Iowa; O'Brien Industrial Equipment Co., Inc., San Francisco, California; Bepex Corp., Minneapolis, Minnesota (sold under the tradename TURBOFLEX, also described in U.S. Patent 4,810,099) or the like.
- the preferred particle sizes included in the granules of this invention are those passing through a 12 mesh screen and retained upon an 80 mesh screen. As noted above, it is preferred that less than about 15% of the granules pass through an 80 mesh screen. Particles which are larger than will pass through a 12 mesh screen may be ground to reduce their size to the desired range thereby increasing the efficiency of the process.
- the drying operation may take any suitable form such as fluid bed, tray, rotary or other means typically employed to dry granules.
- the drying temperature employed is usually in the range of from 50°C to 75°C.
- Each drying apparatus will affect the apparent bulk density, particle size distribution and surface absorptivity characteristics of the finished product, the granulated NTA. It was found that granular NTA produced using a vacuum drying system had a higher surface absorptivity and a lower bulk density than granular NTA produced using a fluid bed drying system.
- the granular product When prepared in accordance with this invention the granular product is compatible with modern detergent formulations commonly known as concentrated detergents.
- a density of at least 0.6g/cc and preferably 0.7g/cc can be blended successfully with the more dense, concentrated detergent ingredient containing surfactant and other additives typically incorporated into heavy duty laundry detergents such as optical brighteners, antiredeposition agents, corrosion inhibitors, dyes and pigments.
- the granules of this invention may also be blended with other builders such as carbonates, citrates, sulfates, silicates and zeolites.
- the absorptivity of granules produced by addition of sulfuric acid to NTA so as to partially neutralize the NTA or of granules produced by the addition of an aqueous alkali metal silicate to NTA was determined by the following procedure. Into a 400 ml beaker was placed 50g of granules to be tested. A 25 ml buret was filled with a non-ionic liquid surfactant, a linear alcohol alkoxylate commercially available from BASF under the tradename Plurafac D25. In a drop-wise manner the surfactant was added to the beaker while stirring with a scoopula.
- a non-ionic liquid surfactant a linear alcohol alkoxylate commercially available from BASF under the tradename Plurafac D25.
- Surfactant droplets must be mixed with the test granules until the granules are sufficiently "wet". This is determined by forming a trough in the wetted granules with the scoopula and no granules fall into the trough when the beaker is tapped on the side with the scoopula at a point 1/4 distance from the bottom from a distance of approximately 10,2 cm (4 inches) away from the beaker. The amount of surfactant added to the granules at this point is read from the buret and the absorptivity calculated on the basis of ml/100g of granules.
- NTA powder used is trisodium nitrilotriacetate monohydrate sold commercially by Monsanto Company.
- a charge of 45.36 kg of NTA powder was placed into the agglomerator.
- 4.762 kg of a 5% sulfuric acid solution was sprayed onto the falling film of granules and then 4.309 kg of 98% sulfuric acid was sprayed onto the film for a total addition time of 30 minutes for both additions.
- the batch was then mixed for an additional 10 minutes for a ratio of addition time/mix time of .75.
- the agglomerated material was dried in a fluid bed dryer at 50°C for 30 minutes.
- the mesh size and fraction percent of the total weight obtained appears in Table I below.
- the bulk density of the -12 mesh to +80 mesh portion was found to be 0.71 g/cc and the absorptivity as determined by the above described absorptivity test was found to be 14.1 ml/100g.
- the flow rate was 121.1 ml/sec indicating that the granules did not cake after being subjected to a standard caking test in a glass container at 100% humidity for 48 hr.
- the -12 to +80 mesh portion of the granules had a density of 0.73 g/cc and an absorptivity of 14.2 ml/100g.
- a Stephan Machine Corporation UMC-5 mixer was employed and the blade speed was set at 900 rpm.
- a charge of 750.3g of NTA powder was placed into the mixer.
- 250g of RU® Silicate was added to the NTA powder during an addition time of 30 seconds.
- the batch was then mixed for an additional 30 seconds.
- the agglomerated or granulated material was dried in a fluid bed dryer at 60°C for 30 minutes.
- the mesh size and fraction percent of the total weight obtained appears in Table XI below.
- the bulk density of the -12 mesh to +80 mesh portion of the granules was found to be 0.71 g/cc and the absorptivity as determined by the above described absorptivity test was found to be 7.0 ml/100g.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Absorbent Articles And Supports Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Fertilizers (AREA)
Abstract
Description
US-A-3 717 589 describes particulate spray-dried detergent additives containing a mixture of sodium nitrilotriacetate and a second material selected from the group of crystalline modifiers, water-dispersible polymers, film formers and pH modifiers. The film formers can be represented by low level of sodium silicate but are preferably represented by surfactant and quasi-surfactant materials.
Mesh Size | Fraction % |
1.68 mm (+12) | 14.95 |
0.841 mm (+20) | 19.70 |
0.420 mm (+40) | 22.78 |
0.250 mm (+60) | 14.47 |
0.177 mm (+80) | 8.39 |
0.149 mm (+100) | 6.27 |
0.074 mm (+200) | 13.45 |
Mesh Size | Fraction % |
+12 | 35.86 |
+20 | 18.67 |
+40 | 20.52 |
+60 | 11.23 |
+80 | 4.16 |
+100 | 2.58 |
+200 | 6.98 |
Mesh Size | Fraction % |
+12 | 19.24 |
+20 | 25.79 |
+40 | 27.55 |
+60 | 12.97 |
+80 | 4.422 |
+100 | 2.80 |
+200 | 7.22 |
Mesh Size | Fraction % |
+12 | 13.80 |
+20 | 22.16 |
+40 | 13.09 |
+60 | 12.01 |
+80 | 12.23 |
+100 | 10.12 |
+200 | 16.60 |
Mesh Size | Fraction % |
+12 | 26.53 |
+20 | 20.65 |
+40 | 12.75 |
+60 | 9.51 |
+80 | 11.38 |
+100 | 5.69 |
+200 | 13.49 |
Mesh Size | Fraction % |
+12 | 4.73 |
+20 | 22.79 |
+40 | 36.35 |
+60 | 16.88 |
+80 | 5.55 |
+100 | 4.03 |
+200 | 9.67 |
Mesh Size | Fraction % |
+12 | 27.57 |
+20 | 23.28 |
+40 | 22.58 |
+60 | 15.66 |
+80 | 5.76 |
+100 | 3.18 |
+200 | 1.96 |
Mesh Size | Fraction % |
+12 | 5.78 |
+20 | 12.24 |
+40 | 15.70 |
+60 | 15.43 |
+80 | 13.81 |
+100 | 10.66 |
+200 | 26.38 |
Mesh Size | Fraction % |
+12 | 4.73 |
+20 | 22.79 |
+40 | 36.35 |
+60 | 16.88 |
+80 | 5.55 |
+100 | 4.03 |
+200 | 9.67 |
Mesh Size | Fraction % |
+12 | 35.19 |
+20 | 26.98 |
+40 | 20.30 |
+60 | 8.43 |
+80 | 2.26 |
+100 | 1.26 |
+200 | 5.57 |
Mesh Size | Fraction % |
+12 | 20.4 |
+20 | 34.7 |
+40 | 29.7 |
+60 | 12.9 |
+80 | 1.4 |
+100 | 0.3 |
-100 | 0.6 |
Mesh Size | Fraction % |
+12 | 16.9 |
+20 | 30.1 |
+40 | 19.7 |
+60 | 15.7 |
+80 | 8.1 |
+100 | 3.9 |
-100 | 5.6 |
Mesh Size | Fraction % |
+12 | 20.2 |
+20 | 28.3 |
+40 | 27.3 |
+60 | 17.5 |
+80 | 4.7 |
+100 | 1.2 |
-100 | 0.9 |
Mesh Size | Fraction % |
+12 | 20.2 |
+20 | 28.3 |
+40 | 27.3 |
+60 | 17.5 |
+80 | 4.7 |
+100 | 1.2 |
-100 | 0.9 |
Mesh Size | Fraction % |
+12 | 14.4 |
+20 | 43.4 |
+40 | 19.9 |
+60 | 10.2 |
+80 | 4.1 |
+100 | 5.5 |
-100 | 2.5 |
Claims (14)
- A process for preparing granular alkali metal nitrilotriacetate (NTA) which comprises,(1) Contacting NTA powder with an aqueous alkali metal silicate solution,(2) Mixing the wetted NTA to form granules, and(3) Drying the granules characterized in that:
a majority of the granules, by weight, are in the 1.68 mm to 0.177 mm (-12 to +80 mesh) size range and have a density of at least 0,60 g/cc and an absorptivity in the absorptivity test greater than 7 ml/100g. - The process of Claim 1 wherein the alkali metal silicate is a sodium silicate.
- The process of Claim 1 wherein at least 50% of the granules produced are in the size range of from -12 to +60 mesh.
- The process of Claim 1 wherein the granules are dried at a temperature in the range of from 50°C to 60°C.
- The process of Claim 1 wherein the weight ratio of the alkali metal silicate to alkali metal nitrilotriacetate is in the range of from 0.17 to 0.40.
- The process of Claim 5 wherein the weight ratio of the alkali metal silicate to alkali metal nitrilotriacetate is in the range of from 0.25 to 0.35.
- A granular alkali metal nitrilotriacetate (NTA) produced by the addition of an aqueous powder alkali metal silicate solution to powder NTA, characterized in that:
said granular NTA is composed of agglomerated NTA particles, the granular NTA having a density within the range of from 0.6 g/cc to 0.81 g/cc, an absorptivity in the absorptivity test greater than 7 ml/100g and a particulate size distribution in which a majority of the granules arc within a range from 1.68 mm to 0.250 mm in size (-12 to +60 U.S. mesh size). - The granular alkali metal nitrilotriacetate of Claim 7 wherein the absorptivity in the absorptivity test is greater than 12 ml/100g.
- The granular alkali metal nitrilotriacetate of Claim 7 wherein the aqueous alkali metal silicate solution is a sodium silicate solution.
- A granular alkali metal nitrilotriacetate (NTA) comprising granules characterized in that:
said granules are composed of agglomerated NTA particles, wherein said NTA granules having a density within the range of from 0.6g/cc to 0.81g/cc, an absorptivity in the absorptivity test greater than 7 ml/100g and a particulate size distribution in which a majority of the granules are within a range of from 1.68mm to 0.250mm in size (-12 to +60 U.S, mesh size) and wherein the granular NTA has a weight ratio of alkali metal silicate to NTA in the range from 0.17 to 0.40. - The granular alkali metal nitrilotriacetate (NTA) of claim 10 wherein the absorptivity in the absorptivity test is greater than 12 ml/100g.
- The granular alkali metal nitrilotriacetate (NTA) of claim 10, wherein; the granular NTA has a weight ratio of alkali metal silicate to NTA in the range from 0.25 to 0.35.
- A granular alkali metal nitrilotriacetate (NTA), wherein; said granular alkali metal nitrilotriacetate is the product of The process comprising:(1) mixing powdered nitrilotriacetate with an aqueous alkali metal silicate solution so as to form granules of agglomerated nitrilotriacetate powder and;(2) drying said granules wherein:(i) said granular NTA has a particle size distribution in which the majority of the granules arc in the range from 1.68mm to 0.250mm;(ii) said granular NTA has an absorptivity in the absorptivity test of at least 7 ml/100g:(iii) said granular NTA has a density within the range from 0.6 g/cc to 0,81 g/cc, and;(iv) said granular NTA has a weight ratio of alkali metal silicate to NTA in the range from 0.17 to 0.40.
- The process of claim 13 wherein the ralio of alkali metal silicate to alkali metal nitrilotriacetate is from 0.25 to 0.40.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16268593A | 1993-12-03 | 1993-12-03 | |
US162685 | 1993-12-03 | ||
PCT/US1994/013652 WO1995015370A1 (en) | 1993-12-03 | 1994-12-01 | Granular alkali metal nitrilotriacetate |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0731833A1 EP0731833A1 (en) | 1996-09-18 |
EP0731833B1 true EP0731833B1 (en) | 2001-10-24 |
Family
ID=22586704
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95904155A Expired - Lifetime EP0731833B1 (en) | 1993-12-03 | 1994-12-01 | Granular alkali metal nitrilotriacetate |
EP95904154A Expired - Lifetime EP0731832B1 (en) | 1993-12-03 | 1994-12-01 | Process for producing granular alkali metal nitrilotriacetate |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95904154A Expired - Lifetime EP0731832B1 (en) | 1993-12-03 | 1994-12-01 | Process for producing granular alkali metal nitrilotriacetate |
Country Status (6)
Country | Link |
---|---|
US (2) | US5861531A (en) |
EP (2) | EP0731833B1 (en) |
AT (2) | ATE207526T1 (en) |
CA (2) | CA2177607A1 (en) |
DE (2) | DE69428803D1 (en) |
WO (2) | WO1995015370A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5861531A (en) * | 1993-12-03 | 1999-01-19 | Solutia, Inc. | Process for producing granular alkali metal nitrilotriacetate |
KR0151876B1 (en) * | 1994-11-30 | 1998-10-01 | 엄길용 | Thin film transistor for lcd and its making method |
EP0880577A1 (en) * | 1996-02-12 | 1998-12-02 | Unilever N.V. | Nta/edta-containing detergent composition |
US6635612B1 (en) * | 1999-10-01 | 2003-10-21 | The Procter & Gamble Company | Process for delivering chelant agglomerate into detergent composition for improving its storage stability, flowability and scoopability |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3546123A (en) * | 1968-03-04 | 1970-12-08 | Monsanto Co | Granular products containing disodium nitrilotriacetate and process for producing same |
WO1995015369A1 (en) * | 1993-12-03 | 1995-06-08 | Monsanto Company | Process for producing granular alkali metal nitrilotriacetate |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3591630A (en) * | 1968-03-04 | 1971-07-06 | Monsanto Co | Caking-resistant granular sodium nitrilotriacetates and processes for producing the same |
US3629329A (en) * | 1968-03-04 | 1971-12-21 | Monsanto Co | Process for producing granular alkali metal nitrilotriacetate |
US3717589A (en) * | 1970-09-17 | 1973-02-20 | Monsanto Co | Sodium nitrilotriacetate and processes for producing same |
JPS4910194A (en) * | 1972-05-30 | 1974-01-29 | ||
US3901831A (en) * | 1973-08-24 | 1975-08-26 | Monsanto Co | Method of making dense detergent granules |
DE3111617A1 (en) * | 1981-03-25 | 1982-10-07 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING MIXED GRANULES FROM CONDENSED PHOSPHATES AND FRUIT SALTS |
DE3504628A1 (en) * | 1985-02-11 | 1986-08-14 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING GRANULATE GRANULATE |
US4810099A (en) * | 1987-05-06 | 1989-03-07 | Berwind Corporation | Mixer |
ATE134381T1 (en) * | 1990-11-30 | 1996-03-15 | Rhone Poulenc Chimie | BUILDING MATERIAL BASED ON ALKALINE METAL SILICATES FOR CLEANING AGENT COMPOSITIONS |
-
1994
- 1994-12-01 US US08/656,219 patent/US5861531A/en not_active Expired - Fee Related
- 1994-12-01 AT AT95904155T patent/ATE207526T1/en not_active IP Right Cessation
- 1994-12-01 WO PCT/US1994/013652 patent/WO1995015370A1/en active IP Right Grant
- 1994-12-01 DE DE69428803T patent/DE69428803D1/en not_active Expired - Lifetime
- 1994-12-01 WO PCT/US1994/013651 patent/WO1995015369A1/en active IP Right Grant
- 1994-12-01 EP EP95904155A patent/EP0731833B1/en not_active Expired - Lifetime
- 1994-12-01 DE DE69428210T patent/DE69428210D1/en not_active Expired - Lifetime
- 1994-12-01 CA CA002177607A patent/CA2177607A1/en not_active Abandoned
- 1994-12-01 EP EP95904154A patent/EP0731832B1/en not_active Expired - Lifetime
- 1994-12-01 AT AT95904154T patent/ATE205247T1/en not_active IP Right Cessation
- 1994-12-01 US US08/647,959 patent/US5744639A/en not_active Expired - Lifetime
- 1994-12-01 CA CA002177608A patent/CA2177608A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3546123A (en) * | 1968-03-04 | 1970-12-08 | Monsanto Co | Granular products containing disodium nitrilotriacetate and process for producing same |
WO1995015369A1 (en) * | 1993-12-03 | 1995-06-08 | Monsanto Company | Process for producing granular alkali metal nitrilotriacetate |
Also Published As
Publication number | Publication date |
---|---|
EP0731832B1 (en) | 2001-09-05 |
DE69428210D1 (en) | 2001-10-11 |
ATE207526T1 (en) | 2001-11-15 |
CA2177607A1 (en) | 1995-06-08 |
US5744639A (en) | 1998-04-28 |
WO1995015370A1 (en) | 1995-06-08 |
DE69428803D1 (en) | 2001-11-29 |
EP0731832A1 (en) | 1996-09-18 |
EP0731833A1 (en) | 1996-09-18 |
WO1995015369A1 (en) | 1995-06-08 |
US5861531A (en) | 1999-01-19 |
CA2177608A1 (en) | 1995-06-08 |
ATE205247T1 (en) | 2001-09-15 |
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